MNL45-EB/Apr.

2002

Radiation Curing

Introduction
BEFORETHE EARLY1970S, there was little apparent concern or even awareness
of the amount of solvent that entered the atmosphere from coatings and allied products. As a result, in the early 1970s over 90% of applied industrial
coatings were low solids in nature. That is, they contained from 10% to 20%
by weight solids, excluding pigments or other suspended materials, and the
remainder was solvent. Industrial coatings at that time were typified as being "low solids and solvent borne." Architectural coatings, commonly
known as house paints and varnish, were also solvent borne, and latexes
were really just coming into commercial reality. In those days, many people
said that latexes did not have the quality of oil-based paints--many latex
paints did not. Today, latex house paints are prevalent, but because of their
excellent application characteristics and properties, oil-based paints still have
a solid place in the market. However, their slow drying nature and odor remain as deficiencies. Even latex paints are relatively slow drying.
One would like to think industry could readily see the many advantages of changing from a single, high-polluting technology to a multitechnology arrangement that would provide forward thinking. Thinking that
would lead to cost savings as well as resource conservation, while being
ecologically friendly and simultaneously providing a healthier work and
community environment. Actually, at that time the slow moving coating industry could not or would not see the future--sales and use of solvent
dominated the picture.
H o w much solvent was used in a coating formulation in the early 1970s?
When the total solids content was 10%, nine pounds of solvent were used
with one pound of final coating material. When the total solids content was
20%, four pounds of solvent were used with one p o u n d of final coating material. These large quantities of relatively inexpensive solvent resulted in excellent application characteristics, flow, and leveling of the liquid coating,
and in high gloss, thin, continuous films of the relatively expensive, final
solid polymeric coating. Pleasing decorative and functional coatings r e 1

Copyright92002 by ASTM International

www.astm.org

RADIATION CURING OF COATINGS

sulted. But huge quantities of solvent were spewing into the atmosphere, and
both industry and the public seemed oblivious to this fact.
At this time there were several reasons for the state of affairs in the coating industry being one of solvent-borne, low solids. Petroleum-derived solvents and the energy, which is also fossil-fuel based, needed to evaporate
them were inexpensive. This is easy to realize if one recalls that, prior to the
early 1970s, oil and petroleum products had not yet seen the effect of cartel
pricing. At the time, if someone had proposed a scenario in which the price
of oil w o u l d increase b y a factor of 10 to 25 times, they w o u l d have been told
to quit wasting time and pose something realistic. No one wanted to imagine
the effect such pricing would have on the coating industry or on individuals.
Unless one lived through it, it is difficult to visualize the pressures that were
brought to bear on the general public and industry through dictated
petroleum shortages that ended up as long lines at gasoline stations and
markedly increased prices. Not only did consumers feel the stress of waiting
in gasoline lines, they felt the even sharper stress of wondering if they w o u l d
be able to purchase fossil fuel-based products at any price to heat their homes
and drive to their place of employment or on vacation. In the coating industry, companies that had large drying ovens became concerned with the problem of what to do if they couldn't operate their ovens--they knew heating of
homes would come first. There was enough oil and natural gas, but it was
only available at a high, cartel-set price. And the price of oil went up and up
in what seemed a never-ending spiral.
A complicating effect superimposed on the price/availability picture
was the fact that solvents were an excellent medium for reducing the viscosity of high molecular weight polymers to an application viscosity. At that
time, most polymers used for coatings had high molecular weight. This was
a necessary requirement to achieve the high-quality performance characteristics expected from the liquid coatings that were most often used as lacquers.
This factor was the major reason large quantities of solvent were used in formulations. Then, almost overnight, oil cost and availability became a serious
problem. To satisfy ecological concerns of certain groups, the matter was exacerbated when the government set requirements on the coating industry.
The industry was to quickly formulate 80% solids coatings. That is, they were
to change from using about four or more pounds of solvent for each p o u n d
of final coating to one-fourth of a p o u n d of solvent per each pound of final
coating--a factor of 16 or more decrease!
It was in this crucible of market pressures, the Clean Air Act of 19701,
and existing old know-how that the new technologies of water-borne, highsolids, powder, and radiation-curable coatings, along with the various sub1The USA Environmental ProtectionAgency'sClean Air Act of 1970was amended in 1977
and 1990,but at the time under discussion, it was the original act that was the driving force.

Radiation Curing

categories such as two-package high solids, w a t e r dilutable coatings, highersolids coatings, and the like, w e r e born.
As might be expected, there were m a r k e d l y different opinions regarding
each of these n e w technologies. M a n y t h o u g h t solvent-borne systems w o u l d
n e v e r be replaced, and in the long run, they were losers. Others thought water-borne coatings were the answer. These w e r e usually p e o p l e w h o were in
the architectural latex-coating business, and they felt it w o u l d be easy to develop industrial latex coatings. High-solids coatings s e e m e d an easy w a y to
meet the d e m a n d s of the Clean Air Act. All one h a d to d o was decrease
molecular weight and high solids could be achieved. They temporarily forgot or just did not k n o w molecular w e i g h t - p r o p e r t y relationships, and they
found that systems to be satisfactorily cross-linked n e e d e d functionality suitably located on each molecule to ensure they w o u l d be incorporated into the
final coating film network. Others thought p o w d e r and radiation w o u l d be
important, but these were m o r e difficult to achieve and often did not receive
as m u c h attention from the i n d u s t r y at that time.
In the end all the n e w technologies f o u n d a place in industry. The only
parts of i n d u s t r y that did not gain from the changes b r o u g h t about b y the
n e w technologies were those w h o refused to be forward-looking and clung
to the old ways. N e w companies came into being, names changed, and consolidations took place as the n e w technologies f o u n d their niche in the marketplace. Today, radiation curing is well established and appears to be poised
to make great strides into this m a r k e t [1].

What is Radiation Curing and Why is it Used?

Radiation curing of coatings, inks, adhesives, and sealants 2 is the effectively
instantaneous conversion of a usually liquid, low viscosity formulation of ingredients that has been applied to a substrate and exposed to a radiation
source into a p o l y m e r i z e d a n d cross-linked mass with decorative a n d / o r
functional properties. This process usually results in an effectively complete
conversion of the liquid formulation into a solid, useful product, i.e., radiation-cured coatings are essentially 100% solids in nature. Radiation as used
in the radiation curing i n d u s t r y is usually ultraviolet radiation (photons or
photocuring) or electron b e a m e n e r g y (electrons or E-beam curing), h o w ever, coherent or laser radiation and visible radiation 3 or light are also used.
2 Coatings, inks, adhesives, and sealants can be and are cured with radiation. In this book,
the word "coatings" will be taken to be generic to all of these products, unless one is specifically
dealing with one of the others. Currently, radiation curing of sealants has limited use. This is primarily due to the need for curing through a considerable thickness of sealant material. Readers
interested in radiation curing of sealants might consider the information in the topic "Thick Section Curing" found in Chapter 11.
3 Webster's New Collegiate Dictionary defines light as that part of the electromagneticspectrum of radiation that is visible to the human eye.

RADIATION CURING OF COATINGS

"Radcure" is an adjective derived to describe anything that has to do with radiation-curing technology--applications, equipment, materials, and so on.
When a material is exposed to radiation, it is "irradiated." Although radiation and its nature will be discussed in a following section, a few words about
it are appropriate at this time.
The electromagnetic spectrum is made up of electromagnetic waves of
radiation that are identified by fluctuations of electric and magnetic fields. It
comprises the total range of electromagnetic wavelengths, k, and extends
from essentially zero to infinity. If numbers are to be placed on these wavelengths, it could be said that they range from about 10 -13 to 103 meters. Cosmic rays, gamma rays, and hard X-rays are on the low end of the range, and
microwave, radio, radar, television, and electric waves are on the high end of
the range [2,3]. Contained within the electromagnetic spectrum is the visible
portion of the spectrum, wavelengths from 400 to 760 nanometers or from violet to red, that is known as "light," and the invisible portion of the spectrum
just beyond the violet end of the visible region that is known as "ultraviolet"
and often referred to as "ultraviolet light." The ultraviolet region of wavelengths extends from about i to 400 nanometers, and it contains a region from
about 15 to 280 nanometers known as "Ultraviolet C," another from 280 to
320 nm known as "Ultraviolet B," and another region from 320 to 400 nm
known as "Ultraviolet A"[4]. Ultraviolet B is radiation that causes the phenomenon known as "sunburn" and prolonged exposure to it over many
years can cause skin cancer. Ultraviolet C radiation is very powerful and is
used to sterilize surfaces because it has the ability to kill bacteria and viruses.
The range from 800 to about 30 000 nanometers is known as the infrared region of the spectra. Above this begins the microwave region and so on.
RadTech International has somewhat different, but similar, designations of
the ultraviolet radiation ranges. These can be found in the RadTech Glossary
of Terms at the end of this volume.
Why does industry use the radiation curing process? Many of the attributes of this process can be summarized as:
9 Low capital investment
9 Low energy consumption and cost
9 High solids and elimination of solvents
9 Plastics and other heat sensitive substrates can be coated and cured
9 Rapid cure and high productivity
9 Multiple operations are possible
9 Space requirements are low
9 Use of existing equipment when retrofitting radiation equipment
9 High degrees of cross-linking and, therefore, potential for improved abrasion, chemical, and stain resistance.
Capital investment is low for ultraviolet curing or photocuring equipment. The equipment usually can be designed to meet specific needs, and no

Radiation Curing

" d e a d " or u n u s e d curing areas n e e d be involved. If electron b e a m technology

is involved, capital investment can be high, but it is used w h e n high, largev o l u m e p r o d u c t i o n c o u p l e d with v e r y high line speeds is involved. N e w
small-scale electron b e a m systems h a v e e x p a n d e d the electron b e a m techn o l o g y into the realm of relatively m o d e s t cost.
Radiation-curing systems have low p o w e r requirements, and little heating of the substrate takes place. N o large ovens are required for evaporation
of solvent or water. These factors result in low operating costs, a factor that
takes o n ever increasing importance as the price of fuel u n d e r g o e s m a r k e d increases, as it did in 2000. A n additional benefit is that the systems r u n c o o l
and this i m p r o v e s the working e n v i r o n m e n t for e m p l o y e e s b y m a k i n g ambient t e m p e r a t u r e s quite reasonable and easier to control. It is also easier and
less time-consuming to change over a finishing line from one formulation or
design pattern to another, which results in increased cost savings and productivity.
As m e n t i o n e d earlier, radiation-curing systems are either 100% solids or
v e r y high solids in nature. VOC 4 is near zero, since all of the formulation reacts or remains effectively with the final film. For particular end uses, there
are specialized formulations to which solvent is a d d e d for viscosity reduction, b u t it is usually easy to stay within regulatory limits or to fit the equipm e n t with a solvent r e c o v e r y system. Water-borne radiation curable systems
are also used.
Heat-sensitive substrates such as plastics, printed circuit boards and assemblies, paper, w o o d , and the like can be coated and cured with radiation
technology. The reason for this is that there is little b u i l d u p of heat in the substrate w h e n thin coating films are involved. If thick films are prepared, judicious selection of f o r m u l a t i o n i n g r e d i e n t s - - p a r t i c u l a r l y p h o t o i n i t i a t o r
l e v e l - - a n d line speed can be used as controls to r e m o v e concerns about heat
buildup. This factor can be of particular utility in the electronics industry.
I m p r o v e d economics and efficiency result from the "instantaneous" curing characteristics of radiation-cured systems. D e p e n d i n g on the nature of
the formulation being cured, line speeds of h u n d r e d s of feet per rain can be
easily achieved [7]. This results in increased production. W h e n this is coupled with the fact that multiple operations can be accomplished in a single
pass t h r o u g h a finishing line, plant o u t p u t is often doubled, tripled, or m o r e
on a line that is no longer and often shorter b y 100 to 200%, or more than a
conventional finishing line. That is, a substrate can be printed in one or m o r e
colors, the ink cured, o v e r coated with a clear finish, cured, turned o v e r in a
4 VOC is art abbreviation for Volatile Organic Compounds that is used by the USA Environmental Protection Agency (EPA). VOC is defined as "Any organic compound that participates in atmospheric photochemical reactions; that is, any organic compound other than those
the Administrator designates as having negligible photochemical reactivity." Details about VOC
and how it is measured can be found in the literature [5, 6].

RADIATION CURING OF COATINGS

"Ferris wheel" arrangement, and then coated and cured on the reverse side.
Of course, elimination of solvent also represents a calculable cost savings.
Savings result because there is no need for solvent, handling solvent, evaporating solvent, recovering solvent, and for safely and ecologically sound disposing of recovered solvent in some manner.
In general, space requirements are much less, often 25-50% less, for a radiation-curing line than for a conventional coating line. The main reason for
this is that no large ovens are required for evaporation of solvent a n d / o r water. In addition, there is no need for a solvent recovery system. An additional
space-saving feature of radiation-curable coatings is their 100% solids nature.
Less drums of formulated coating are required when solvent is eliminated,
which also results in decreased handling.
At times, existing coating lines can be retrofitted with radiation-curing
equipment. This can be accomplished with minor adaptations and costs, particularly with photocuring equipment, which can be very versatile in nature.
It can be readily understood that radiation-curing lines can run much
faster than conventional coating lines. When this is coupled with the multiple operations that can be accomplished on a single pass through the line,
marked increases in productivity can be attained. For these and the other reason discussed, radiation curing is a technology that is currently in vogue and
that will be experiencing growth of about 10% compounded in the future [8].

Radiation
In the above, there was a brief introduction to radiation and its relationship
to the electromagnetic spectrum. Radiation is the propagation a n d / o r emission of rays through space, which is effectively a void, or through a medium,
such as air, in the form of either waves or particulate emission. Just what does
this mean?
Most people think of activating molecules by using thermal energy as
the normal w a y for chemical phenomena to occur. That is, temperature elevation is used to push molecules up a hill or over a barrier and allow them to
attain a different, higher energy state. For example, the conversion of something from the liquid state to the gaseous state is usually accomplished with
the use of thermal energy. In the coating industry, many thermal processes
or thermally activated reactions are used. Such phenomena usually use thermal energy, whose source is an increase of temperature, to increase one or
more of the rotational, translational, and vibrational energy states from a
ground state to the upper range of their energy distribution [9]. One of the
simplistic processes used in the coating industry is evaporative drying of a
lacquer that usually is accomplished with supplied heat or thermal energy.
The liquefaction and flow of powder coatings is also accomplished with thermal energy. Another specific example is the crosslinking reaction of hexam-

Radiation Curing 7

ethoxymelamine with hydroxyl functionality that is accomplished b y supplying thermal energy to the system. Various other thermal processes used
in the coating industry should be readily apparent to readers.
Thermal processes such as these are inefficient in terms of energy usage
and of the amount of final coating applied to a substrate for a given unit of
energy. A more efficient w a y to supply and utilize the energy necessary to effect a change to an activated or reactive state is to bring the molecules directly
into contact with "packets" of energy supplied by sources such as neutrons,
B-rays or high velocity electrons, o~-particles, or the quanta of electromagnetic
energy termed "photons" and supplied by that portion of the electromagnetic spectrum known as ultraviolet radiation or b y light. A distinct advantage of photochemically induced reactions over thermally induced reactions
is selectivity. Different and particular reactions of the same substance can be
promoted by irradiating it with different frequencies of ultraviolet or visible
radiation. Investigation of the reactions caused b y such energy-supplying
processes is termed "radiation chemistry." The process used to effect cure of
coatings, inks, adhesives, and sealants with radiation chemistry is known as
"radiation curing." If only ultraviolet or visible radiation is used, the particular process is known as "photochemistry." In industry, the two main methods of effecting radiation curing are electron beams and ultraviolet radiation.
Equipment for curing with these two methods will be discussed in Chapter
2.
An electron b e a m is a stream of electrons that are emitted by a source.
The electrons all move at the same speed and in the same direction. An electron beam, which is similar to a cathode-ray tube, produces the stream of
electrons. The cathode is heated to generate electrons, a high-voltage system
then directs the electron stream, and electromagnets guide the stream to the
substrate. This technique was mainly used for high volume production because of equipment cost and size. In a general sense, selection between ultraviolet and electron beam curing is dependent on factors such as film thickness, pigmentation or opacity, production scale or volume, and similar items.
Photochemistry is a subdivision of radiation chemistry, and it is the science of the chemical changes that are initiated by ultraviolet and visible radiation on molecules. The particular wavelength region of ultraviolet that is
of interest in the coating area is from about 100 to 400 nm, but more practically from about 200 to 400 nm. It should be understood that incident ultraviolet radiation can be transmitted, absorbed, or refracted, but it is only absorbed radiation that can produce a chemical change in molecules. This is the first
law of photochemistry, which is known as the Grotthuss-Draper Law. Certain compounds can absorb particular ultraviolet wavelengths or energy
packets and are completely transparent to other ultraviolet rays. Another
w a y of stating this is that if a molecule does not absorb radiation of a particular frequency, it will not undergo a photochemical change when contacted
with radiation of that particular frequency. The amount of radiation ab-

RADIATION CURING OF COATINGS

sorbed by a compound is proportional to the thickness of the compound's

surroundings. The second law of photochemistry, or Stark-Einstein Law,
tells us that only one molecule of a radiation absorbing system will be activated for each photon of radiation absorbed by a chemical system. The quantity of photochemical reaction that takes place is determined by the product
of time of exposure and the radiation intensity.
The fact that radiation is energy can be simply and readily exemplified.
The following examples quickly and vividly demonstrate that ultraviolet and
visible radiation are energy. It is well known that sunlight contains wavelengths from both the ultraviolet and the visible spectra. Almost everyone
has taken a magnifying lens and focused the sun's rays onto paper or a similar material. When this is done, it is observed that the focused beam of
broad-spectrum radiation quickly raises the temperature of the paper to the
kindling point, and smoke begins to rise. Another example is the fact that
when the ultraviolet rays in sunlight bombard our skin, they cause reddening or tanning as well as other less apparent, long-term changes. The fact that
ultraviolet rays are not absorbed or reflected by the same media as other
forms of energy, such as visible or light energy, is apparent from the "sunburn" one can obtain on a cloudy day. The ultraviolet rays are transmitted
through the cloud moisture, whereas much of the other sun's rays are absorbed or reflected by the cloud, and a darkening or dimming effect and a
cooling effect are observed.
Other commonly known, but perhaps not realized as such, photochemical reactions include photography wherein light converts silver bromide to
metallic silver, vision in which a protein is isomerized by radiation in the
retina of the eye, and photosynthesis wherein photons from sunlight are absorbed by chlorophyll and make energy available for the formation of various chemicals such as carbohydrates, vanillins, phenolics, and so on. Thus, it
is readily apparent that ultraviolet and visible radiation, as well as other portions of the electromagnetic spectrum, are energy. However, at this point the
magnitude of the energy, its nature, and its mode of transmission are not apparent.

Simplified Classic to Modern Light/Radiation/Energy Theory

In the Seventeenth Century, there were two concepts used to describe the
nature of light and ultraviolet radiation. In one of these concepts, Newton
posed a corpuscular or particle theory for such radiation. This theory was
generally accepted until almost the end of the Eighteenth Century. At this
time, Huygens posed the second concept, and it considered such radiation
to be wave-like in nature. Studies concerned with the diffraction, interference, reflection, and refraction phenomena that occur with light took place

Radiation Curing

in the early N i n e t e e n t h Century, a n d the results of these studies could be

best explained b y i n v o k i n g the H u y g e n s w a v e theory. Further credence
w a s g i v e n to the w a v e - l i k e character theory w h e n it w a s f o u n d that, in a
v a c u u m , light travels at the s a m e velocity as that o f other electromagnetic
radiation, n a m e l y 3 101~ c m 9s -1.
In the 1860s, M a x w e l l p r e s e n t e d his electromagnetic theory, in w h i c h radiation e n e r g y is described as a c o m b i n a t i o n of oscillating electrical a n d m a g netic fields positioned at right angles or n o r m a l to each other. T h e n the ene r g y p r o p a g a t e s t h r o u g h o t h e r w i s e e m p t y s p a c e or a m e d i u m w i t h the
velocity of light in the direction of p r o p a g a t i o n . M a x w e l l ' s theory g a v e further acceptance to the w a v e t h e o r y of H u y g e n s . H o w e v e r , e v e n t h o u g h such
p h e n o m e n a could b e explained b y o n l y i n v o k i n g the w a v e theory, the p h o toelectric effect 5 a n d other light characteristics could not be explained with
o n l y the w a v e theory. To u n d e r s t a n d these p h e n o m e n a , it w a s necessary to
b r i n g into p l a y the c o r p u s c u l a r or p a c k e t theory.
Studies b y Planck [10] at the b e g i n n i n g of the T w e n t i e t h C e n t u r y indicated that a b o d y radiating light w i t h a f r e q u e n c y v w o u l d radiate e n e r g y
only in w h o l e n u m b e r multiples of hv, w h e r e h, Planck's constant = 6.624
X 10 27 erg" S, is the p r o p o r t i o n a l i t y b e t w e e n energy, E, a n d f r e q u e n c y with:
E = h u =hc/A

w h e r e c is the velocity 6 of light in a v a c u u m a n d k is the w a v e l e n g t h . Planck's

h y p o t h e s i s also stated that a b o d y could only a b s o r b e n e r g y in e v e n n u m b e r
multiples of hr. A f e w years later Einstein [12] d e v e l o p e d his relativity expression,
E = mc 2,

w h e r e i n m is m a s s a n d c is as p r e v i o u s l y d e f i n e d . H i s efforts e x t e n d e d
Planck's theory, a n d they indicated that electromagnetic radiation is quantized a n d m a d e u p of discrete q u a n t a or p h o t o n s each of which, as a unit of
energy, has a v a l u e hr. Thus, a p h o t o n is a q u a n t u m of electromagnetic ene r g y of a single w a v e l e n g t h , i.e., of a single m o d e of direction a n d polariza5 When a photon impinges onto a surface and is absorbed, an electron may be emitted from
the surface. This emission of an electron is the means by which photons can be detected and is
known as the photoelectric effect.
6 Usually the velocity of light is thought of as a constant; however, in January 2001, it was
reported that physicists were able to stop light and then send it on its way at 3 10~~cm's-1.
Atoms of gas were magnetically chilled to within a few millionths of a degree from absolute
zero. Two laser beams that operated at different frequencies were directed into the gas, wherein
it imprinted a pattern into the orientation of the spinning atoms of sodium and rubidium. As the
intensity decreased, the probe light dimmed and then vanished, but still was imprinted on the
metals where it was frozen or stored. When the control beam was restored, the light stored in the
spinning atoms was reconstituted and continued on its way [11].

10

RADIATION

CURING OF COATINGS

tion. 7 From these investigations, the modern concept of radiation emerged as

energy with a dual nature. Radiation moves through space in wave packets
(corpuscles) that have a spectrum of energies (i.e., wavelengths) with wavelike properties.
Earlier it was pointed out that an advantage of curing with ultraviolet or
visible radiation is selectivity. For a change to take place, the product of the
frequency of the radiation that is absorbed by a molecule and Planck's constant must exactly match the energy that separates the ground state of the
molecule, Eg, and the excited state, Ee.
E = h v = (E~ -

Eg)

If the frequency is changed, the magnitude of E changes; and if a state

Ee - E~ equal to the new magnitude of E exists for the molecule, the molecule
will be transformed to this new and different state. Thus, by varying the frequency of radiation impinging on a molecule, it is possible to get photochemical reactions that are completely different from each other, assuming a
number of excited states exist for the molecule. As was mentioned earlier, the
electromagnetic spectrum encompasses a very broad range of wavelengths
that are between about 10 -13 to 10 3 meters [18].

Magnitude of Ultraviolet and Visible Radiation Energy

With this picture of radiation and how it functions, we can now turn to calculation of the magnitude of the energy associated with ultraviolet and visible radiation. As described above, Planck's constant is the proportionality
constant between the energy of a photon and wavelength, and the energy at
7 This has been a simplistic discussion of the relationship between radiation and energy. It
is beyond the scope of this book to deal with the transition from this information into details of
the various theories involved. However, a short discussion may help direct interested readers in
understanding radiation and provide literature references that are pertinent to the topic.
Rutherford [13] theorized that the atom was a dense, charged nucleus with surrounding orbiting electrons. This picture required the orbiting electrons to lose energy through radiation,
and thus, spiral into the nucleus. Bohr [14] altered Rutherford's picture by placing the electrons
into fixed orbits that had different energy levels. His theory of the hydrogen atom had the sole
electron in this atom occupying particular, discrete energy levels with the energy state determined by a principle quantum number, n, with n having a whole integer value. The theory
worked well for single electron materials, but it was not capable of dealing with atoms that contained more than one electron. When the electron moved from a higher energy level, E2, to a
lower level, El, a quantum of radiation was emitted. The frequency of the emitted radiation was
given by E = E2 - E1 = hr.
About two decades later, in 1924, de Broglie [15] suggested that the dual nature of radiation
might also be true for matter. That is, any moving corpuscle, radiation or matter, has a wavelength associated with it and that a similar relationship exists between m o m e n t u m and the
wavelength of bodies other than light quanta with ~= h/mv. This was later confirmed for electrons by Thomson and others [16,17].

Radiation Curing 11

any particular wavelength, E( can be calculated from

= Iq [6626 quantum sec][ l

This energy is the specific energy associated with the wave packet that
has a wavelength/t. Quite often, chemists are interested in the energy that is
associated with a mole of material or with the energy associated with a mole
of quanta. This quantity of energy has been termed an "Einstein" and is equal
to Avogadro's number, 6.023 1023, times the energy associated with a particular wavelength. So, if we make this change and substitute for the velocity
of light, the expression becomes
E(~) =

[ 6.6256 10-27 erg 9 sec ]

quantum
X[6:023

quantum][2.9979 x 101~cm][1 ]
mole
][
~ec

1023

jk j

or

E(x) =

[11963mole0 e 8 cm][l1

with the wavelength expressed in centimeters. Since the wavelength is usually expressed in nanometers, and since one joule, J, is equal to i 107 ergs,
the expression for energy can be expressed as
[1.1963 X 108 erg 9 cm ][ 107 n m ]
E(x) = L
mole
jl_~j
I 1 j~
]IX
n-~J
1 107 ergs

1"1963 108 j~
X
mole

in terms of joules per mole and as

[1.1963 x 108 joules][. 1 kcal ] _ 2.8592 104 kcal
E(x) = [
k mole
J[ 4184 joules J
k
mole
in terms of kilocalories per mole. Values of E(~) at various wavelengths are
given in Table 1.1. The energy required to rupture a double bond and form a
T A B L E 1.1. M a g n i t u d e of E n e r g y at Various W a v e l e n g t h s .
ENERGY PER MOLE
WAVELENGTH,
)t
JOULES 10-s
KILOCALORIES
100
11.96
286.00
200
5,98
143.00
300
3.99
95.3
71.5
400
2.99
500
2.39
57.2
700
1,71
40.9

12 RADIATION CURING OF COATINGS

free radical depends on the particular chemical molecule receiving the energy. It is usually on the order of 10-80 Kcal per mole (0.42-3.35 x 105
J/mole)) [19], which may be compared with the values in Table 1.1.

P h o t o n Production
A photon is the quantum of electromagnetic energy of a single wavelength.
Photons are produced in the ultraviolet and visible radiation regions by
9 spontaneous or stimulated radiation transitions between electronic energy
levels in atoms or molecules,
9 recombination of two radiative bodies as in electron-ion recombination,
and
9 electron retardation wherein radiation is emitted w h e n an electron is
forced to deviate from its normal path as occurs when an electron passes
near a positive ion.
If it is possible for an atom to exist in two energy states, E~ and E2 with
E 2 ~ El, there are three possible radiation processes that can connect the two

energy levels. There can be a simple, uncomplicated absorption in which the

atom at energy level E1 is placed in a radiation field that contains wavelength
K, where K = hc/(E2 - El). Here, it may absorb a photon and be excited to a
higher energy level E2. Induced or stimulated emission occurs when an atom
that exists in energy state E2 is placed in a radiation field that contains wavelength K, where again ;~ is given by hc/(E2 - El). A photon may impinge on
the atom and cause it to emit a photon that is coherent with the impinging
photon. When this happens, the energy level drops to El. Spontaneous emission is a third method of photon generation. In this process, an atom in a
higher energy state E2 can spontaneously emit a photon and drop to energy
level E 1. These mechanisms lead to the photons or quanta that activate photoinitiators that, as we shall see in ensuing chapters, cause polymerization of
reactive species in the formation of radiation~cured coatings.

Electrons
It is important to point out that electrons are not included in the electromagnetic spectrum. Electrons differ from photons in that they are particulate and
not wave-like in nature, and they have mass. Because of their mass, accelerated electrons as formed by an electron beam apparatus have the ability to
penetrate matter. These phenomena, as well as the depth of penetration into
materials, are further discussed in Chapter 2. Photons, which are included in
the electromagnetic spectrum, can also penetrate matter. The depth of penetration depends on their energy, wave, and particulate nature.

Radiation Curing

13

References
[1] Koleske, J. V., "RadTech 2000," Paint and Coating hldustry Magazine, Vol. 16, No. 6, June
2000, p. 34.
[2] Kinstle, J. F., "Radiation Polymerization," Paint and Varnish Production, Vol. 63, No. 6, June
1973, p. 17.
[3] Lake, R. T., "Ultraviolet Curing of Organic Coatings," Radiation Curing, Vol. 10, No. 2, 1983,
p. 18.
[4] Davis, T. W., "Ultraviolet Radiation," Microsoft| Encarta| Online Encyclopedia2000.
[5] Glossaryfor Air Pollution Control of Industrial Coating Operations, EPA-450/3-83-013R, Environmental Protection Agency, Washington, DC, December 1983.
[6] Brezinski, J. J., Manual on Determination of Volatile Organic Compounds in Paints, Inks, and Related Coating Products, MNIA, ASTM International, West Conshohocken, PA, 1993.
[7] Schaeffer, W. B., "UV Curable Materials Response and its Relationship to Power Level and
Lamp Spectra," Proceedings, Volume 1, RadTech "90-North America, March 25-29, 1990, p. 29.
[8] Lawson, K., "Status of UV/EB Curing in North America-2000," RadTech 2000, Baltimore,
MD, April 12, 2000.
[9] Moore, W. J., Physical Chemistry, 2nd ed., Prentice Hall, Inc., NJ, 1955.
[10] Planck, M., Annalen der Physik, Vol. 1, 1900, p. 69; Annalen der Physik, VoL 4, 1901, p. 553.
[11] "Physicists Bring Light to a Stop Then Send It on Its Way," Sci-Tech, www.foxnews.com,January 19, 2001.
[12] Einstein, A., Annalen der Physik, Vol. 17,1905, p. 132.
[13] Rutherford, E., PhilosophicalMagazine, Vol. 21, 1911, p. 669.
[14] Bohr, N., PhilosophicalMagazine, Vol. 26, 1913, p. 476.
[15] de Broglie, L., PhilosophicalMagazine, Vol. 47, 1924, p. 446.
[16] Thompson, G. P., ProceedingsRoyal Society, Al17, 600, 1928.
[17] Davisson, C. and Germer, L. H., Physics Review, Vol. 31, 1927, p. 705.
[18] Commission Internationale de l'Eclairage, "International Lighting Vocabulary," CIE, Paris,
1970.
[19] Ridyard, Andrew, "Accurate, High Power UV Spectral Measurement," Proceedings of
RadTech 2000, Baltimore, MD, 9-12 April, 2000, p. 136.